Technical Field of the Invention
[0001] This invention relates to a composition of a color-recovering agent for recovering
the color of clothes having a colored pattern, which can be used generally in home.
Prior Arts
[0002] Fade of clothes having a colored pattern proceeds through repeated washing and wear
under the influence of sunrays and chlorine in tap water. To recovery the color, the
present applicants disclose, in JP-A No. 3-180578, an aerosol agent for deepening
fiber colors. Such a composition can be sprayed to eliminate the luster of clothes
caused by rubbing with hard surfaces of desks, chairs, etc. thereby deepening the
color thereof.
[0003] Further, JP-A No. 53-111192 and JP-A No. 55-26232 disclose a method of industrially
deepening the color of clothes by allowing a low-refractive compound to be adsorbed
into stained clothes and heating or wet-heating the clothes, thereby deepening the
color thereof.
[0004] On one hand, JP-A No. 10-96172 discloses a method of allowing silicone to be adsorbed
into fibers. Further, JP-A No. 5-508889 discloses a composition for a cloth softener
agent comprising amino-modified silicone. However, the object of these inventions
is to confer smoothness and water repellency on clothes, but not to improve the color
of clothes.
[0005] Further, JP-A No. 62-174298 describes treatment of faded clothes with an aqueous
solution containing cellulase to recover the color of the clothes, but the effect
is not satisfactory.
Disclosure of the Invention
[0006] The object of this invention is to provide an agent, which in home can easily recover
the color of clothes faded by repeated washing, etc.
[0007] This invention relates to a color-recovering agent composition which comprises (a)
a water-insoluble polymer with a refractive index of 1.20 to 1.45 at 25°C, (b) at
least one compound selected from components (i) and (ii) below defined and (c) water,
wherein the ratio by weight of (a)/(b) is in the range of 3/1 to 100/1:
(i) a compound with a molecular weight of 300 to 1,000 having, in the molecule thereof,
at least one member selected from the group consisting of an amide group, an ester
group, a quaternary ammonium group and a tertiary amino group and at least one of
a C10-36 alkyl or alkenyl group, and
(ii) a polymer or copolymer derived from at least one ethylenically unsaturated compound
having at least one member selected from the group consisting of an amide group, a
carboxylic acid group, a hydroxyl group, a quaternary ammonium group and a tertiary
amino group.
[0008] In one aspect of this composition, the component (a) is a water-insoluble silicone
compound, and the component (b) is a compound with a molecular weight of 300 to 1,000
having, in the molecule thereof, at least one of a quaternary ammonium group and a
tertiary amino group and at least one of a C
10-36 alkyl group and a C
10-36 alkenyl group.
[0009] In the composition of this invention, the component (a) is preferably a fluorine-containing
polymer or a silicone compound.
[0010] The composition can further comprise (d) a non-aqueous medium or (e) an emulsifier.
The composition of this invention may also be a composition comprising the components
(a), (b), (c), (d) and (e) described above.
[0011] As used herein, "refractive index" is the one measured by an Abbe refractometer,
and "water-insoluble" refers to a solubility of not higher than 1 g/L ion-exchanged
water at 20°C.
Detailed Description of the Invention
[0012] Hereinafter, this invention is described in more detail.
Component (a)
[0013] The component (a) in this invention is a water-insoluble polymer having a refractive
index at 25°C of 1.20 to 1.45, preferably 1.25 to 1.45, and particularly preferably
1.30 to 1.43. When the refractive index is in this range, a sufficient color-recovering
effect can be obtained, and color can also be made suitable. A water-soluble polymer
cannot give the color-recovering effect achieved by the water-insoluble polymer of
this invention.
[0014] The polymer satisfying the properties described above is preferably a fluorine-containing
polymer and a silicone compound. The fluorine-containing polymer is preferably a polymer
or copolymer of at least one monomer selected from trifluoroethyl acrylate (or methacrylate),
pentadecafluorooctyl acrylate (or methacrylate), tetrafluoroethylene, trifluorochloroethylene,
trifluoroethyl acrylate (or methacrylate), hexafluoropropylene, tetrafluoroethylene
oxide and hexafluoropropylene oxide, or modified silicone containing an organic group
including a fluoroalkyl group, fluoroalkylene group or fluoroaryl group as described
later (referred to hereinafter as fluorine-modified silicone) . For the effect of
recovering color, these polymers preferably have a weight-average molecular weight
of 1,000 to 1,000,000, preferably 1,500 to 500,000 as determined by gel permeation
liquid chromatography using polystyrene as the standard with dimethylformamide as
the development solvent.
[0015] The fluorine type compound can be obtained by an usual radical polymerization reaction
when the monomer is an ethylenically unsaturated compound, or by an usual addition
reaction when the monomer is an alkylene oxide compound. The radical polymerization
reaction may be bulk polymerization, solution polymerization or emulsion polymerization.
The polymerization initiator used may be 2,2'-azobis(2-amidinopropane), azobisisobutyronitrile,
di-t-butyl peroxide, hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide,
methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid,
lauroyl peroxide or persulfate.
[0016] The addition reaction of the alkylene oxide compound can be easily carried out in
the presence of a catalyst a usually used alkali such as sodium hydroxide or potassium
hydroxide or Lewis acid such as boron trifluoride.
[0017] In this invention, the fluorine type polymer may be a copolymer containing copolymerizable
monomers other than fluorine-containing monomers, wherein the molar ratio of fluorine-containing
monomers to the total monomers is 0.5 or more, preferably 0.6 or more, for the effect
of recovering color.
[0018] When the fluorine-modified silicone is used, the viscosity thereof at 25°C is 100,000
to 200,000 mm
2/s, preferably 500,000 to 100,000 mm
2/s and particularly preferably 500 to 80,000mm
2/s, for the effect of recovering color. The viscosity can be measured, for example,
by an Ubbellohde U-shaped viscometer.
[0019] In this invention, a silicone compound can also be used as the component (a). The
silicone compound is an organopolysiloxane oil having refractive index and solubility
in the above-specified ranges, and specifically mention is made of a dimethyl polysiloxane
oil (referred to hereinafter as dimethyl silicone), an organopolysiloxane oil derived
from dimethyl silicone oil by replacing some methyl groups in side chains or in terminals
thereof by hydroxyl groups (referred to hereinafter as hydroxy silicone) or an organopolysiloxane
oil derived from the dimethyl silicone oil or hydroxy silicone by replacing some methyl
groups (preferably some methyl groups in side chains) by "organic groups other than
methyl groups" (referred to hereinafter as modified silicone). The modified silicone
is illustrated mainly in chapter 6 in Silicone Handbook (first edition, edited by
Kunio Ito and published on August 31, 1990 by the Nikkan Kogyo Shimbun, Ltd.). The
organic groups other than methyl groups include organic groups including an amino
group, organic groups including an amide group, organic groups including a polyether
group, organic groups including an epoxy group, organic groups including a carboxy
group, organic groups including an alkyl group and organic groups including a halogenoalkyl
group, halogenoalkylene group or halogenoaryl group, as well as organic groups including
a poly(N-acylalkylene imine) chain. The silicone compound in this invention is preferably
modified silicone having organic groups including an amino group (referred to hereinafter
as amino-modified silicone), modified silicone having organic groups including a poly
(N-acylalkylene imine) chain or modified silicone having organic groups including
a halogenoalkyl group, halogenoalkylene group or halogenoaryl group (halogeno-modified
silicone), more preferably amino-modified silicone or halogeno-modified silicone having
an amino equivalent of 1,500 to 40,000 g/mol, preferably 2,500 to 20,000 g/mol and
particularly preferably 3,000 to 10,000 g/mol, and most preferably amino-modified
silicone.
[0020] The silicone compound used is preferably modified silicone having organic groups
including an amino group or a poly(N-acylalkylene imine) chain, more preferably modified
silicone having an amino group or a poly(N-acylalkylene imine) chain bound via a C
2-8 alkylene group to a side chain of the polysiloxane chain.
[0021] When modified silicone having water-soluble organic groups is used in this invention,
the one modified to have a solubility of 1 g or less/L of ion-exchanged water is selected.
[0022] The silicone compound (excluding fluorine-modified silicone) in this invention is
a compound having a weight-average molecular weight of preferably 1,000 to 1, 000,
000, more preferably 3, 000 to 500, 000 and most preferably 5,000 to 250, 000 as determined
by gel permeation liquid chromatography using polystyrene as the standard with chloroform
as the development solvent. The viscosity thereof is preferably 10 to 100,000 mm
2/s, more preferably 500 to 50,000 mm
2/s and most preferably 1,000 to 40,000 mm
2/s. The viscosity can be measured, for example, by an Ubbellohde U-shaped viscometer.
Component (b)
[0023] The component (b) in this invention is a compound selected from the following (i)
or (ii):
(i) a compound with a molecular weight of 300 to 1,000 having, in the molecule thereof,
at least one member selected from the group consisting of an amide group, an ester
group, a quaternary ammonium group or a tertiary amino group and at least one of a
C10-36 alkyl group and alkenyl group, and
(ii) a polymer or copolymer derived from at least one ethylenically unsaturated compound
having at least one member selected from the group consisting of an amide group, a
carboxylic acid group, a hydroxyl group, a quaternary ammonium group or a tertiary
amino group.
[0024] The compound (i) is particularly preferably (i-1) a quaternary ammonium salt of the
general formula (2) below, (i-2) a tertiary amine compound of the general formula
(3) or (4) below, (i-3) an ester compound of a C
2-10 polyvalent alcohol with a C
10-20 fatty acid, (i-4) an amide compound of a polyvalent carboxylic acid with a secondary
amine having a C
10-20 alkyl group, and (i-5) an amide compound of a C
10-20 fatty acid with an alkylene diamine, dialkylene triamine or hydroxyalkyl alkylene
diamine.
wherein R
4 represents a C
10-36, preferably C
10-24' more preferably C
12-18 alkyl or alkenyl group, R
6 and R
7 each represent a C
1-3 alkyl group or hydroxyalkyl group or R
4-(X-R
5)
n-; R
8 represents a C
1-3 alkyl group or hydroxyalkyl group; X is a group selected from -COO-, -OCO-, -CONR
9- and -NR
9CO-; R
5 represents a C
1-5, preferably C
1-3 alkylene group; R
9 represents a hydrogen atom or a C
1-3 alkyl group or hydroxyalkyl group; n is an integer of 1 or 0; and Y
- is an inorganic or organic anion, preferably a halogen ion, sulfate ion, phosphate
ion, C
1-3 alkyl sulfate ion, C
1-12 fatty acid ion, more preferably a halogen ion and C
1-3 alkyl sulfate ion.
wherein R
10 represents a C
10-36, preferably C
10-24, more preferably C
12-18 alkyl or alkenyl group; R
12 and R
13 each represent a C
1-3 alkyl group or hydroxyalkyl group or R
10-(X-R
11)
m-; X is a group selected from -COO-, -OCO-, -CONR
9- and -NR
9CO-; R
11 represents a C
1-5, preferably C
1-3 alkylene group; m is an integer of 1 or 0; and R
9 represents a hydrogen atom or a C
1-3 alkyl group or hydroxyalkyl group.
wherein R
14, R
15, R
18, R
21 and R
22 independently represent a hydrogen atom, a C
1-5 alkyl group or hydroxyalkyl group or R
23-(W-R
24)
l-, and at least one of R
14, R
15, R
18, R
21 and R
22 is R
23-(W-R
24)
l-, whereupon R
23 is a C
10-36 alkyl group, and R
24 is a C
1-5 alkylene group; W is -COO-, -OCO-, -CONR
25-, -NR
25CO-, or -O-, and W and R
24 in R
23-(W-R
24)
l- bound to each N atom may be the same or different; R
25 represents a hydrogen atom, a C
1-3 alkyl group or hydroxyalkyl group; R
16, R
17, R
19 and R
20 each represent a C
1-5 alkylene group; each of l and m is a number of 0, 1 or 2; Y and Z may be the same
or different and each represent a group selected from -COO-, -OCO-, -CONR
26-, -NR
26CO-, -O- and -CH(OR
27)-; R
26 and R
27 each represent a hydrogen atom or a C
1-5 alkyl group or hydroxyalkyl group; and k is a number of 0 to 10 on average.
[0025] The ester compound (i-3) of a C
2-10 polyvalent alcohol with a C
10-20 fatty acid is preferably a mono-, di- tri- and/or tetra-ester of a C
10-22, preferably C
10-20, more preferably C
12-18 saturated or unsaturated fatty acid with glycerin, pentaerythritol, sorbitol, ethylene
glycol, propylene glycol, diethylene glycol or dipropylene glycol, or a mixture of
such esters, or glyceryl ether or diglyceryl ether having at least one C
10-20, preferably C
12-18 alcohol added thereto, or a mixture thereof, or an ester compound of a C
10-20, preferably C
12-18 fatty acid with a C
1-20, preferably C
1-18 alcohol. Among these, ester compounds of glycerin, pentaerythritol or sorbitol with
a C
12-18 fatty acid, or a mixture thereof, are preferable.
[0026] The amide compound (i-4) of a polyvalent carboxylic acid with a primary amine includes
amide compounds of a C
10-20, preferably C
12-18 primary amine with a polyvalent carboxylic acid selected from oxalic acid, glutaric
acid, succinic acid, maleic acid, fumaric acid, valeric acid, adipic acid, azelaic
acid, sebacic acid, brassylic acid, dodecane diacid, tricarballylic acid, 1,2,3-propane
dicarboxylic acid, citric acid, malic acid and tartaric acid.
[0027] The amide compound (i-5) of a C
10-20 fatty acid with ethylene diamine, diethylene triamine or hydroxyethyl ethylene diamine
is also good. The amine compound may be fully or partially amidated.
[0028] The compound belonging to (i) in this invention is particularly preferably (i-1),
(i-2) and (i-3) for the effect of recovering color, more preferably (i-1) and (i-2).
[0029] Further, the compound (ii) is preferably a polymer or copolymer having a weight-average
molecular weight of 1,000 to 2,000,000, preferably 3,000 to 1,500,000 (as determined
by gel permeation chromatography using polyethylene glycol as the standard) obtained
by a polymerization reaction usually using at least one member selected from amide
type monomers such as acrylamide, methacrylamide, crotonic acid amide and vinyl pyrrolidone,
carboxylic acid type monomers such as acrylic acid, methacrylic acid and maleic acid,
hydroxyl type monomers such as polyvinyl alcohol, quaternary ammonium type monomers
such as acryloyl aminopropyl trialkyl ammonium salt, methacryloyl aminopropyl trialkyl
ammonium salt, acryloyloxyethyl trialkyl ammonium salt, methacryloyloxyethyl trialkyl
ammonium salt, dialkyl diallyl ammonium salt and trialkyl allyl ammonium salt, and
amine type monomers such as acryloyl aminopropyl dialkyl amine, methacryloyl aminopropyl
dialkyl amine, acryloyloxyethyl dialkyl ammonium salt, and methacryloyloxyethyl dialkyl
amine, particularly preferably a polymer or copolymer having a weight-average molecular
weight of 5,000 to 1,500,000, preferably 10,000 to 1,000,000 containing at least one
of the above amide type monomers and quaternary ammonium type monomers in an amount
of 20 to 100 mole %, preferably 40 to 100 mole % in the polymer.
[0030] The above-mentioned (ii) may be a copolymer of the above ethylenically unsaturated
monomer with a copolymerizable unsaturated monomer, and such an unsaturated monomer
includes alkyl (meth)acrylate, ethylene, propylene, butadiene, styrene and fatty acid
vinyl. For the effect of recovering color, the copolymerizable unsaturated monomer
is contained in an amount of less than 50 mole %, preferably less than 30 mole % and
particularly preferably less than 10 mole % in the copolymer (ii).
[0031] For the effect of recovering color, the color-recovering agent of this invention
preferably comprises the component (a) in an amount of 1 to 30% by weight, particularly
2 to 20% by weight, and the component (b) in an amount of 0.1 to 10% by weight, particularly
0.2 to 5% by weight. Further, the ratio by weight of (a)/(b) is preferably 3/1 to
100/1, more preferably 3/1 to 50/1, most preferably 4/1 to 25/1.
Component (c)
[0032] The component (c) in this invention is preferably water from which heavy metals ion
and hard-water components had been removed, particularly preferably ion-exchanged
water or distilled water. Desirably, the color recovering agent of this invention
comprises the component (c) in an amount of 40 to 95% by weight, preferably 50 to
90% by weight and more preferably 60 to 90% by weight for storage stability.
Component (d)
[0033] The component (d) in this invention includes ethylene glycol, propylene glycol, diethylene
glycol, dipropylene glycol, alkyl glyceryl ether, di- or trialkylene glycol monoalkyl
ether, di- or trialkylene glycol monoallyl ether, triethylene glycol monoallyl ether,
glycerine, 1,6-hexane diol, 2,5-hexane diol, cyclohexanol, 2-hexanol and 1-octanol.
[0034] Among these, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
C
3-8 alkyl glyceryl ethers, di- or trialkylene glycol mono- or diallyl ether, and di-
or triethylene glycol mono- or diphenyl ether are particularly preferable. In particular,
at least one member selected from ethylene glycol, propylene glycol, ethanol and propanol
is compounded preferably for the effect of recovering color and storage stability.
The color-recovering agent of this invention comprises the component (d) in an amount
of preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight.
Emulsifier (referred to hereinafter as component (e))
[0035] Because the component (a) in this invention is water-insoluble, an emulsifier is
preferably blended for the purpose of emulsification and dispersion in the color-recovering
agent. A part of the component (b) acts as an emulsifier. Further, the composition
preferably contains an emulsifier other than the component (b).
[0036] The component (e) as the emulsifier includes anionic surfactants such as alkyl benzene
sulfonic acids or salts thereof, alkyl sulfates, polyoxyalkylene alkyl ether sulfates,
olefin sulfonates, alkane sulfonates and fatty acid salts, nonionic surfactants such
as polyoxyalkylene alkyl or alkenyl ethers, polyoxy alkylene alkyl phenyl ethers,
fatty acid alkanol amides or alkylene oxide adducts thereof, sucrose fatty acid esters
and alkyl glucosides, and amphoteric surfactants such as amine oxides, sulfobetaine
and carbobetaine.
[0037] A polyoxyalkylene alkyl (C
8-20) or alkenyl (C
8-20) ether having 5 to 100 molecules on average of alkylene oxide added thereto is preferable.
[0038] Specifically, the emulsifier in this invention is particularly preferably a nonionic
surfactant represented by the general formula (1):
R
1-O-(R
2O)
p-H (1)
wherein R
1 is a C
8-20, preferably C
10-20 alkyl group or alkenyl group; R
2 is a C
2-3 alkylene group, preferably an ethylene group; and p is a number of 2 to 200, preferably
5 to 100, more preferably 5 to 80.
[0039] The compound of the general formula (1) includes the following compounds:
R
3-O-(C
2H
4O)
r-H
wherein R
3 is a C
10-18 alkyl group, r is a number of 5 to 60, preferably 5 to 40;
R
3-O-(C
2H
4O)
s(C
3H
6O)
t-H
wherein R
3 has the same meaning as defined above; s and t independently represent a number of
2 to 40, preferably 2 to 40, and the sum of s and t is a number of 5 to 60; and ethylene
oxide and propylene oxide may be added in a random or block manner.
[0040] The ratio by weight of component (e)/component (a) in this invention is preferably
1/1,000 to 2/1, more preferably 5/1,000 to 1/1, particularly preferably 1/100 to 1/1
for emulsification and dispersion stability. The diameter of the emulsified particles
in the color-recovering agent is 0.01 to 5 µm, preferably 0.02 to 3 µm and particularly
preferably 0.01 to 1 µm for color recovery.
[0041] Other components such as perfumes, bactericides, anti-fungus agents, pigments, and
viscosity regulators may be incorporated into the color-recovering agent of this invention
insofar as the effect of this invention is not deteriorated.
Composition
[0042] The color-recovering agent of this invention is used in the form of a dispersion
prepared by diluting the components (a), (b) and preferably (d) with water [component
(c)].
[0043] The pH value (at 20°C) of the color-recovering agent of this invention is 2 to 9,
preferably 3 to 8.0, for storage stability and the effect of recovering color.
[0044] Further, this invention also relates to a color recovering composition which comprises
(a) a water-insoluble polymer with a refractive index of 1.20 to 1.45 at 25°C, (b)
a compound with a molecular weight of 300 to 1,000 having at least one of a quaternary
ammonium group and a tertiary amino group and at least one of a C
8-36 or C
10-36 alkyl group and a C
8-36 or C
10-36 alkenyl group, and (c) water. The composition preferably comprises the component
(a) in an amount of 5 to 50% by weight, particularly 2 to 20% by weight and the component
(b) in an amount of 1 to 10% by weight, particularly 1 to 5% by weight for the effect
of recovering color. Further, the ratio by weight of (a)/(b) is in the range of preferably
3/1 to 100/1, more preferably 3/1 to 50/1 and most preferably 4/1 to 25/1.
Using method
[0045] The color-recovering agent of this invention may be used by soaking faded clothes
therein or by adding it to a neutral detergent or to a generally used weakly alkaline
detergent in washing of clothes, or by adding it to rinsing water after clothes are
washed with a detergent, whereby the color of the clothes with a patterned color can
be easily recovered. When used together with a detergent, the color-recovering agent
is used at a concentration of preferably 0.01 to 2% by weight, particularly preferably
0.033 to 0.5% by weight in the washing solution. When added to rinsing water, the
color-recovering agent is used at a concentration of preferably 0.001 to 0.3% by weight,
particularly preferably 0.01 to 0.2% by weight in the washing solution, whereby the
effect of recovering color can be achieved efficiently.
[0046] In this invention, clothes are soaked in an aqueous medium prepared by dissolving
or dispersing the components (a) and (b) and the arbitrary component in water. The
concentration of the component (a) in the aqueous medium is 5 to 2,500 ppm, preferably
30 to 800 ppm, more preferably 50 to 800 ppm.
[0047] Further, the concentration of the component (b) in the aqueous medium is 1 to 800
ppm, particularly 2 to 500 ppm, particularly preferably 5 to 500 ppm.
[0048] Further, the pH value at 20°C of the aqueous medium used in this invention is 5 to
11, preferably 6 to 10.5, particularly preferably 7.5 to 10.5 in respect of the effect
of recovering color.
[0049] The aqueous medium used in this invention may contain a commercial weakly alkaline
detergent, a softener or a detergent such as a textile size or a fiber-treating agent
in addition to the color-recovering agent, and the concentration of these detergents
or the fiber-treating agent is desirably 900 ppm or less, preferably 700 ppm or less,
particularly preferably 500 ppm or less, to achieve the color-recovering effect effectively.
[0050] In this invention, faded clothes are soaked in the aqueous medium in a bath ratio
of 1/2 to 1/500, preferably 1/5 to 1/100. As used herein, the "bath ratio" refers
to the ratio by weight of clothes to the aqueous medium, that is, bath ratio = clothes/aqueous
medium (ratio by weight). Soaking refers to soaking completely clothes, and the clothes
may be soaked in the stationary aqueous medium or in the aqueous medium under stirring.
The soaking time is 1 to 180 minutes, preferably 5 to 120 minutes, particularly preferably
5 to 30 minutes. Further, the temperature of the aqueous medium is 5 to 50°C, more
preferably 10 to 40°C. After soaking, the clothes are dehydrated and air-dried or
dried in an automatic drier. After drying, the clothes may be ironed.
Example 1
<Preparation of the color-recovering agent>
[0051] Using the components (a-1) to (e-1) shown below, the compositions in Table I-1 were
prepared. Each color-recovering agent was prepared by mixing the components in a total
weight of 200 g in the ratio shown in Table 1 in a 200-ml beaker and stirring the
mixture for 4 hours at 300 r/min with a stainless steel agitating blade of 30 mm in
diameter. The diameter of particles in each color-recovering agent thus emulsified
was in the range of 0.02 to 2 µm. The particle diameter was measured with a light-scattering
photometer ELS-800 manufactured by Ohtsuka Denshi Co., Ltd.
(a-1): Polytetrafluoroethyl acrylate (with a refractive index of 1.37 and a molecular
weight of 170,000, prepared by radical polymerization of tetrafluoroethyl acrylate
by azobisisobutyronitrile as the initiator)
(a-2): Polyoxyhexafluoropropylene (Fonburin Y25, with a refractive index of 1.30 and
an average molecular weight of 3000, Nippon Montedison)
(a-3): Fluorine-modified silicone (SH1265, with a refractive index of 1.38 and a viscosity
of 10,000 mm2/s, Toray Dow Corning)
(a'-1): Modified silicone having organic groups having polyether group (TFS4453, with
a refractive index of 1.46 and a viscosity of 1,000 mm2/s, Toray Dow Corning)
(a'-2): Polymethyl methacrylate (with a refractive index of 1.49 and a molecular weight
of 150,000, prepared by radical polymerization of methyl acrylate by azobisisobutyronitrile
as the initiator)
(b-1): N-stearoyl aminopropyl-N,N,N-trimethyl ammonium chloride
(b-2): N-myristyloyloxyethyl-N,N-dimethyl ammonium chloride
(b-3): The compound obtained in Production Example 1 below, represented by the following
formula:
R-NH-(C2H4NH)n-H
wherein R is a hydrocarbon group derived from palm seed oil.
<Production Example 1>
[0052] 21.4 g (0.139 mole) diethyl sulfate and 1.39 moles of 2-oxazoline were dissolved
in 700 g dehydrated ethyl acetate in a 2-L four-necked flask and then heated under
reflux for 5 hours in a nitrogen atmosphere. Then, 444 g (1.11 moles) solution of
50% primary amine having an alkyl composition derived from palm seed oil in ethyl
acetate was added thereto, and after the mixture was heated under reflux for 10 hours,
the ethyl acetate was distilled away under reduced pressure from the reaction mixture.
Then, amide linkages in 400 g of the resultant compound were hydrolyzed, and propionic
acid produced as a byproduct was removed, whereby compound (b-3) was obtained. The
average degree of polymerization thereof was 8 moles and the yield was 95%.
(b-4) : Dimethyl diallyl ammonium chloride polymer (Marcoat 100, with a molecular
weight of 200,000, produced by Cargon)
(b-5): Dehydrating esterification reaction product of 1 mole of glycerin and 2 moles
of fatty acid having a hardened tallow composition
(b-6): Dehydrating amidation reaction product of 1 mole of citric acid and 2 moles
of stearyl amine
(b-7): Dehydrating condensation reaction product of 1 mole of hydroxy ethyl ethylene
diamine and 2 moles of fatty acid having a hardened tallow composition
(d-1): Ethylene glycol
(e-1): Adduct having 3 moles of ethylene oxide, 3 moles of propylene oxide and 2 moles
of ethylene oxide added to lauryl alcohol in this order in a block form
<Preparation of faded clothes>
[0053] Commercial two black cotton polo shirts were washed with a weakly alkaline detergent
in a washing machine (two-chamber washing machine VH-360S1 produced by Toshiba; detergent
concentration, 0.0667% by weight; tap water, 30 L; water temperature, 20°C; washing
for 10 minutes, dehydration for 1 minute, and rinsing for 5 minutes with 30 L running
tap water) . After this procedure was carried out 5 times, the clothes lost the initial
color, to turn whitish as a whole. The clothes were used as faded clothes. The weakly
alkaline detergent used had an average particle diameter of 500 µm (from which particles
of 125 µm or less in diameter and particles of 1, 000 µm or more in diameter had been
removed), an apparent bulk density of 700 g/cm
3 and a composition consisting of 22 weight % sodium linear (C
12-13) alkyl benzene sulfonate, 5 weight % sodium lauryl sulfate, 4 weight % sodium myristate,
5 weight % polyoxyethylene lauryl ether (having 8 molecules on average of ethylene
oxide added thereto), 8 weight % sodium silicate No. 1, 5 weight % sodium polyacrylate
(weight average molecular weight: 10,000), 15 weight % type A zeolite, 15 weight %
sodium carbonate (soda ash), 3 weight % potassium carbonate, 0.5 weight % protease
(Sabinase 12.0T type-W, produced by Novonordisk), 0.5 weight % cellulase (KAC500 produced
by Kao Corporation) and 17 weight % sodium sulfate anhydride ("weight %" is based
on the weight (excluding 7 weight % volatiles) of the detergent.).
<Treatment method 1>
[0054] One suit of the above faded clothes was soaked for 4 minutes in an aqueous solution
containing 0.3 weight % color-recovering agent in Table 1, dehydrated for 1 minute,
then subjected twice to rinsing for 2 minutes and dehydration for 1 minute, dehydrated
again, and dried in a thermostatic chamber at 25°C under 50% humidity for 12 hours.
After this treatment, the recovery of the color of the clothes was compared with the
faded clothes as the control before the treatment by a panel of 10 persons (males
in their thirties) under a white fluorescent lamp and evaluated under the criteria
shown below. ○ was given to an average point of less than 1, □ to 1.0-1.2, Δ to 1.2-1.5,
and × to 1.5 or more.
Evaluation criteria
[0055]
- 0:
- Near to the color of new clothes.
- 1:
- Seems more vivid in color than the control.
- 2:
- Seems equal to the control.
- 3:
- Seems more faded than the control.
<Treatment method 2>
[0056] The above faded clothes were washed with a combination of a weakly alkaline detergent
(the same as the one used in preparation of the faded clothes; the concentration of
the detergent, 0.0667 weight %) and the color-recovering agent (0.3 weight %) in Table
1 (two-chamber washing machine VH-360S1 produced by Toshiba; 30 L tap water was used;
water temperature, 20°C; washing for 10 minutes, dehydration for 1 minute, rinsing
for 5 minutes with 30 L running tap water) . After this procedure was repeated 5 times,
the faded clothes were compared with the faded clothes (control) washed 5 times without
using the color-recovering agent in Table 1 and evaluated in the same manner as in
treatment method 1. The results are shown in Table I-1.
<Treatment method 3>
[0057] One suit of the above faded clothes was subjected to washing/rinsing with running
waster in the same manner as described above, and when rinsing (2) was initiated,
20 g of each of Products 1 to 7 of the Invention was added, and the clothes were stirred
for 2 minutes. Thereafter, the clothes were dehydrated and dried in a thermostatic
chamber at 25°C under 50% humidity for 12 hours. After this procedure was repeated
7 times, the faded clothes were compared with the faded clothes (control) washed 7
times without using the color-recovering agent in Table I-1 and evaluated under the
evaluation criteria in treatment method 1, and as a result, the same excellent color-recovering
effect as in treatment method 1 was achieved.
Example II
<Preparation of the color-recovering agent>
[0058] The compositions in Tables II-1 to II-2 were prepared in the same manner as in Example
I except that the components (a-21) to (e-22) below were used.
(a-21): Amino-modified silicone (KF-8002, with a refractive index of 1.408, a viscosity
of 1,100 mm2/s and an amino equivalent of 1,700 g/mol, Shin-Etsu Chemical Co., Ltd.)
(a-22): Amino-modified silicone (KF-8003, with a refractive index of 1.408, a viscosity
of 1,850 mm2/s and an amino equivalent of 2,000g/mol, Shin-Etsu Chemical Co., Ltd.)
(a-23): Amino-modified silicone (TSF-4707, with a refractive index of 1.405, a viscosity
of 10,000 mm2/s and an amino equivalent of 7,000 g/mol, GE Toshiba Silicones)
(a-24): Modified silicone (refractive index 1.441) having a poly(N-acylalkylene imine)
chain introduced into it obtained in Production Example 1 below.
<Production Example 21>
[0059] 29.7 g (0.193 mole) diethyl sulfate and 153 g (1.54 mole) 2-ethyl-2-oxazoline were
dissolved in 370 g dehydrated ethyl acetate in a nitrogen atmosphere and heated under
reflux for 3 hours to give terminal-reactive poly(N-propionyl ethylene imine). Then,
50% ethyl acetate solution containing 300 g (0.160 mole based on the amino group)
side-chain primary aminopropyl-modified polydimethyl siloxane (molecular weight 9,000;
amine equivalent 1870) was added thereto in one portion and heated under reflux for
12 hours. The reaction mixture was concentrated under reduced pressure, whereby an
N-propionyl ethylene imine-dimethyl siloxane copolymer was obtained as a pale yellow
rubber solid (468 g, yield 97%). The content of dimethyl polysiloxane was 61%, and
the weight-average molecular weight was 102,000. By neutralization titration with
hydrochloric acid in methanol as the solvent, it was confirmed that the amino group
did not remain.
(a'-21): Modified silicone (KF-354, with a refractive index of 1.460 and a viscosity
of 130 mm2/s, Shin-Etsu Chemical Co., Ltd.) having a polyether group introduced into it
(b-21) : The compound obtained in Production Example 22 below, represented by the
following formula:
wherein R is a residue derived from hardened tallow fatty acid by removing its carboxyl
group.
(b-22): The compound obtained in Production Example 22 below, represented by the following
formula:
wherein R is a residue derived from hardened tallow fatty acid by removing its carboxyl
group.
<Production Example 22>
[0060] (b-21) and (b-22) were produced by the following methods (22-1) and (22-2).
(22-1) 66 g of N-(2-hydroxyethyl)-N-methyl-1,3-propylene diamine synthesized from
an adduct of N-methylethanolamine with acrylonitrile by a known method [J. Org. Chem.,
26, 3409 (1960)], and 284 g hardened tallow fatty acid, were charged into a flask
and heated to 180°C. The mixture was heated at that temperature for about 10 hours
while formed water was distilled away, whereby 300 g reaction product based on the
compound (b-21) was obtained. The acid value, saponification value, hydroxyl value,
total amine value and tertiary amine value of the resultant reaction product were
measured, and the composition of the reaction product was examined, indicating that
the reaction product consisted of 86 weight % of dialkyl derivative, 10 weight % of
monoalkyl amide derivative and 4 weight % of unreacted fatty acid. Analysis by gas
chromatography indicated the unreacted N-(2-hydroxyethyl)-N-methyl-1,3-propylene diamine
was contained in an amount of 0.1 weight % in the reaction product.
(22-2) 300 g compound obtained in (22-1) above was dissolved in 60 g industrial alcohol
containing 8-acetylated sucrose and then introduced into an autoclave, and after 0.15
g 2,6-di-tert-butyl-p-cresol (BHT) was added thereto, 28 g methyl chloride was injected
into the mixture. The mixture was reacted at 100°C for about 8 hours, whereby 390
g reaction product based on the compound (b-2) was obtained. The solid content of
the reaction product was 85% by weight, and the degree of quaternarization reaction,
as determined by measuring the amine value thereof, was 96%. The non-quaternarized
amine dialkyl derivative/monoalkyl amide derivative ratio was 85/15 (ratio by weight).
(b-23) The compound obtained in Production Example 23 below, represented by the following
formula:
R-NH- (C2H4NH)n-H
wherein R is a hydrocarbon group derived from palm seed oil.
<Production Example 23>
[0061] 21.4 g (0.139 mole) diethyl sulfate and 1.39 moles of 2-oxazoline were dissolved
in 700 g dehydrated ethyl acetate in a 2-L four-necked flask and then heated under
reflux for 5 hours in a nitrogen atmosphere. Then, 444 g (1.11 moles) of 50% ethyl
acetate solution of a primary amine having an alkyl composition derived from palm
seed oil was added thereto, and after the mixture was heated under reflux for 10 hours,
the ethyl acetate was distilled away under reduced pressure from the reaction mixture.
Then, amide linkages in 400 g of the resultant compound were hydrolyzed, and propionic
acid produced as a byproduct was removed, whereby compound (b-23) was obtained. The
average degree of polymerization was 8 moles and the yield was 95%.
(b-24): Cetyl trimethyl ammonium chloride (Cortamine 60 W, Kao Corporation)
(b-25): Dehydrating esterification reaction product of 1 mole of glycerin and 2 moles
of fatty acids having a hardened tallow composition
(b-26): Dehydrating amidation reaction product of 1 mole of citric acid and 2 moles
of stearyl amine
(b-27) : Dehydrating condensation reaction product of 1 mole of hydroxy ethyl ethylene
diamine and 2 moles of fatty acids having a hardened tallow composition
(d-21): Propylene glycol
(e-21) : Adduct having 5 moles of ethylene oxide added to lauryl alcohol (Emurgen
105, Kao Corporation)
(e-22) : Adduct having 5 moles of ethylene oxide added to C12-14 secondary alcohol.
<Preparation of faded clothes>
[0062] Commercial two navy blue polo shirts (100% cotton) were washed with a weakly alkaline
detergent in a washing machine (two-chamber washing machine VH-360S1 produced by Toshiba;
detergent concentration, 0.0667% by weight; tap water was used; strong stirring; bath
ratio, 1/50 (30 L water); water temperature, 20°C; washing for 10 minutes → dehydration
for 1 minute → rinsing (1) with water for 2 minutes → dehydration for 1 minute → rinsing
(2) with water → dehydration for 1 minute). After this procedure was carried out 7
times, the clothes lost the initial color, to turn whitish as a whole. These clothes
were used as faded clothes. The weakly alkaline detergent used had an average particle
diameter of 500 µm (from which particles of 125 µm or less in diameter and particles
of 1,000 µm or more in diameter had been removed), an apparent bulk density of 700
g/cm
3 and a composition consisting of 22 weight % sodium linear (C
12-13) alkyl benzene sulfonate, 5 weight % sodium lauryl sulfate, 4 weight % sodium myristate,
5 weight % polyoxyethylene lauryl ether (having 8 molecules on average of ethylene
oxide added thereto), 8 weight % sodium silicate No. 1, 5 weight % sodium polyacrylate
(weight average molecular weight: 10,000), 15 weight % type A zeolite, 15 weight %
sodium carbonate (soda ash), 3 weight % potassium carbonate, 0.5 weight % protease
(Sabinase 12.0T type-W, produced by Novonordisk), 0.5 weight % cellulase (KAC500 produced
by Kao Corporation) and 17 weight % sodium sulfate anhydride ("weight %" is based
on the weight (excluding 7 weight % volatiles) of the detergent.).
[0063] <Treatment method 21> was the same as treatment method 1 above.
<Treatment method 22>
[0064] The above faded clothes were washed and rinsed with a combination of a weakly alkaline
detergent (the same as the one used in preparation of the faded clothes; the concentration
of the detergent, 0.0667 weight %) and the color-recovering agent (0.3 weight %) in
Table II-2 in a washing machine under the same conditions as in preparation of the
above faded clothes. To clarify the color-recovering effect, this procedure was repeated
7 times. The faded clothes were compared with faded clothes as the control washed
7 times without using the color-recovering agent in Table 2 and evaluated under the
evaluation criteria in treatment method 1. The results are shown in Table II-2.
<Treatment method 23> was the same as treatment method 3 described above.
<Treatment method 24>
[0065] One suit (300 g) of the faded clothes was placed in a two-chamber washing machine
VH-360S1 produced by Toshiba under the conditions of strong stirring and 30 L tap
water, and after 60 g color-recovering agent in Table 11-2 was introduced into it,
the clothes were washed under stirring for 5 minutes. The treatment solution was discharged,
and the clothes were dehydrated for 3 minutes in a dehydrating chamber in the washing
machine and dried for 12 hours in a room. Recovery of the color of the clothes after
the treatment was compared with that of the faded clothes (control) before the treatment
and evaluated in the same manner as in treatment method 1. The results are shown in
Table II-2.